meso- and β-Pyrrole-Linked Chlorin-Bacteriochlorin Dyads for Promoting Far-Red FRET and Singlet Oxygen Production

A series of chlorin-bacteriochlorin dyads (derived from naturally occurring chlorophyll-a and bacteriochlorophyll-a), covalently connected either through the meso-aryl or β-pyrrole position (position-3) via an ester linkage have been synthesized and characterized as a new class of far-red emitting fluorescence resonance energy transfer (FRET) imaging, and heavy atom-lacking singlet oxygen-producing agents. From systematic absorption, fluorescence, electrochemical, and computational studies, the role of chlorin as an energy donor and bacteriochlorin as an energy acceptor in these wide-band-capturing dyads was established. Efficiency of FRET evaluated from spectral overlap was found to be 95 and 98 % for the meso-linked and β-pyrrole-linked dyads, respectively. Furthermore, evidence for the occurrence of FRET from singlet-excited chlorin to bacteriochlorin was secured from studies involving femtosecond transient absorption studies in toluene. The measured FRET rate constants, k_FRET, were in the order of 10¹¹ s⁻¹, suggesting the occurrence of ultrafast energy transfer in these dyads. Nanosecond transient absorption studies confirmed relaxation of the energy transfer product, ¹BChl*, to its triplet state, ³Bchl*. The ³Bchl* thus generated was capable of producing singlet oxygen with quantum yields comparable to their monomeric entities. The occurrence of efficient FRET emitting in the far-red region and the ability to produce singlet oxygen make the present series of dyads useful for photonic, imaging and therapy applications.     

Annealing effects on the microwave permittivity and permeability properties of Fe79Si16B5 microwires and their micowave absorption performances

This paper reports that amorphous magnetic microwires(Fe79Si16B5) have been fabricated by a melt-extraction technique and have been annealed at 600°C and 750°C respectively.Differential scanning calorimeter measurements show that nanocrystalline magnetic phase(α-Fe) has been formed in the amorphous matrix when it was annealed at 600°C.Hard magnetic phase(Fe2B) was formed in the microwires annealed at 750°C,which increases the magnetic coercivity.Microwave permittivity and permeability are found to be dependent on the microstructures.The permittivity fitting results show that multi Lorentzian dispersion processes exist.For microwires annealed at 750°C,their resonance peaks due to the domain wall movements and natural resonance are found higher than those of microwires annealed at 600°C.The microwave absorption performance of microwires annealed at 600°C is found better than microwires annealed at 750°C.     

Three-dimensional size and orientation of the precipitates in AZ91 magnesium alloys measured by TEM techniques

Knowledge of the microscopic structure, including three-dimensional (3-D) size and orientation of the precipitates, is essential to fully understand the mechanical properties of the magnesium alloys and designing the alloys with better performance. Analytical TEM with high spatial resolution offers the simultaneous measurements of 3-D size, structure, orientation, composition of the precipitates from one typical sample along an established crystallographic axis. Besides popular Burgers orientation relationship (OR), other ORs such as Pitsch--Schrader OR, Crawley OR, Potter OR and a new OR with the form of [0001]_α 1.0° from [311]_γ and (11\bar 20)_α 2.0° from (03\bar 3)_γ between the magnesium matrix and the precipitate γ -Mg₁₇Al₁₂ are identified by TEM imaging and diffraction techniques. As a case study, the thicknesses of the individual precipitates with Burgers OR are further measured to be 100--200~nm through both electron energy-loss spectroscopy and x-ray energy dispersive spectroscopy combining differential x-ray absorption and extrapolation, which are in agreement with the overall 3-D size statistic distribution results obtained through analysing various samples along various directions. Furthermore, the fabricated wedge-shape structure provides a platform on which to study the dependence of the interfacial strain on the variation of the thickness.     

A hybrid trust region algorithm for unconstrained optimization

This paper presents a hybrid trust region algorithm for unconstrained optimization problems. It can be regarded as a combination of ODE-based methods, line search and trust region techniques. A feature of the proposed method is that at each iteration, a system of linear equations is solved only once to obtain a trial step. Further, when the trial step is not accepted, the method performs an inexact line search along it instead of resolving a new linear system. Under reasonable assumptions, the algorithm is proven to be globally and superlinearly convergent. Numerical results are also reported that show the efficiency of this proposed method.     

密度泛函理论研究草甘膦在纯的, 金属原子掺杂石墨烯表面的吸附机理

本研究采用密度泛函理论方法详细讨论了纯的石墨烯及Ti, Fe, Al, Ca原子掺杂石墨烯吸附草甘膦的机理.通过它们之间的吸附能,差分电荷密度,布居电荷,态密度分析发现草甘膦可以被纯的石墨烯及金属原子掺杂石墨烯不同程度地吸附.纯的石墨烯对草甘膦的吸附作用远不及掺杂石墨烯,其中,草甘膦在Ca掺杂石墨烯表面有最强相互作用.这是因为草甘膦与纯的石墨烯之间主要形成了-P=O…π,-COOH…π和-OH…π非共价的相互作用,而与掺杂石墨烯之间主要形成了Metal-O“单齿”和O-Metal-O“双齿”共价相互作用.本研究结果希冀为石墨烯在环境保护方面的应用提供有价值的理论指导.     

Zn1-xTMxO (TM=Al,Ga, In)导电性能的模拟计算

基于密度泛函理论框架下的第一性原理平面波超软赝势方法, 构建了未掺杂与相同掺杂浓度的Zn_1-xTM_xO (TM=Al, Ga, In) 超胞模型,分别对模型进行了几何结构优化、态密度分布和能带分布的计算. 结果表明, 分别高掺杂 (Al, Ga, In) 相同原子分数3.125 at%的条件下, In掺杂对ZnO导电性能最好的结果, 计算结果和实验结果相一致. 关键词： (Al,Ga,In) 高掺ZnO 导电性能 第一性原理     

用自适应MG法,FMG法求解Helmholtz方程

本文针对Ｖ循环、Ｗ循环和多重网格法中最优光滑次数及循环体个数难以确定的缺点，以Ｈｅｌｍｈｏｌｔｚ方程为例给出自适应的多重网格算法和自适应的完全多重网格算法。     

V高掺杂ZnO最小光学带隙和吸收光谱的第一性原理研究

对于V高掺杂ZnO,当摩尔分数为0.0417—0.0625时,随着掺杂量的增加,吸收光谱出现蓝移减弱和蓝移增强两种不同实验结果均有文献报道.采用密度泛函理论的第一性原理平面波超软赝势方法,构建未掺杂ZnO单胞模型、V高掺杂Zn1-xVxO(x=0.0417,0.0625)两种超胞模型,采用GGA+U方法计算掺杂前后体系的形成能、态密度、分波态密度、磁性和吸收光谱.结果表明,当V的掺杂量(原子含量)为2.083%—3.125%时,随着V掺杂量增加,掺杂体系磁矩增大,磁性增强,并且掺杂体系体积增加,总能量下降,形成能减小,掺杂体系更稳定,同时,掺杂ZnO体系的最小光学带隙增宽,吸收带边向低能级方向移动.上述计算结果与实验结果一致.     

The influence of interfacial barrier engineering on the resistance switching of In₂O₃:SnO₂/TiO₂/In₂O₃:SnO₂ device

The I–V characteristics of In2O3:SnO2/TiO2/In2O3:SnO2 junctions with different interfacial barriers are inves- tigated by comparing experiments. A two-step resistance switching process is found for samples with two interfacial barriers produced by specific thermal treatment on the interfaces. The nonsynchronous occurrence of conducting filament formation through the oxide bulk and the reduction in the interfacial barrier due to the migration of oxygen vacancies under the electric field is supposed to explain the two-step resistive switching process. The unique switching properties of the device, based on interfacial barrier engineering, could be exploited for novel applications in nonvolatile memory devices.